CN1122841C - Oxygen sensor an making method - Google Patents
Oxygen sensor an making method Download PDFInfo
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- CN1122841C CN1122841C CN97114948.8A CN97114948A CN1122841C CN 1122841 C CN1122841 C CN 1122841C CN 97114948 A CN97114948 A CN 97114948A CN 1122841 C CN1122841 C CN 1122841C
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 93
- 239000001301 oxygen Substances 0.000 title claims abstract description 93
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 125
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 68
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 5
- 239000010970 precious metal Substances 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 150000002926 oxygen Chemical class 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000007747 plating Methods 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 36
- 239000004020 conductor Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- 230000001681 protective effect Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 6
- 238000005189 flocculation Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000007767 bonding agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910020068 MgAl Inorganic materials 0.000 description 2
- RIWOMFPNVAGRHI-UHFFFAOYSA-N dibenzylideneplatinum Chemical compound C=1C=CC=CC=1C=[Pt]=CC1=CC=CC=C1 RIWOMFPNVAGRHI-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- YNBADRVTZLEFNH-UHFFFAOYSA-N methyl nicotinate Chemical compound COC(=O)C1=CC=CN=C1 YNBADRVTZLEFNH-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
An oxygen sensor element includes a solid electrolyte having cavities on a surface thereof and an electrode formed on the surface of the solid electrolyte. In a method of producing the oxygen sensor element, a solution containing a noble metal compound for nucleus formation is first applied to an electrode forming portion of the solid electrolyte to form a coating film. Then, the coating film is heat-treated to form a nucleus forming portion where noble metal nuclei are deposited. Subsequently, metal plating is applied to the nucleus forming portion to form a plating film deeply entering the cavities. Thereafter, the plating film is burned to form the electrode deeply entering the cavities.
Description
The present invention relates to a kind of oxygen sensing element that is used for the control of motor car engine oil gas ratio, especially relate to a kind of method of making this sensing element.
In the automobile engine tail gas system, with the oxygen concentration in the oxygen sensing element measurement tail gas, so that control the oil gas ratio according to this measured value.
Lambda sensor comprises an oxygen sensing element that is used for detecting oxygen concentration.This oxygen sensing element comprises solid electrolyte and the pair of electrodes that is arranged on this electrolyte, and this is made up of an internal electrode and an outer electrode that is exposed in the tested gas that is exposed in the reference gas electrode.
For above-mentioned this is arranged on the formation zone of solid electrolyte electrode, adopted following method always:
At first, make the electrode of solid electrolyte form the zone and adhere to noble metal nuclear, become the zone to form karyomorphism, plate layer of metal film forming on the nuclear zone then, last, plated film just forms pair of electrodes through sintering on above-mentioned solid electrolyte.
The zone of above-mentioned formation nuclear is to form the zone by the electrode that noble metal (as platinum) is sprayed on solid electrolyte upward to obtain.
Shown in Figure 24 A and 24B, there are a large amount of micropores and pit on the solid electrolyte surface.Therefore, when noble metal nuclear is coated to the lip-deep electrode of solid electrolyte when forming the zone and going up, these noble metal nuclears can enter the zone that these nick holes have formed nuclear, like this when the time to this zone plated film, coating liquid and the nuclear of the noble metal in pit react, plated film and solid electrolyte particle are organically combined, obtain very strong adhesion based on the grappling effect.Plated film is again through oversintering then, just becomes a pair of electrode that is difficult for the sur-face peeling of solid electrolyte.
Yet there is following point in the method that more than forms the nuclear zone:
Specifically, form complicated electrode pattern on the solid electrolyte surface possibly, as Fig. 2 A and shown in Figure 9.Like this,, must make the part mask, so it is just difficult to make the electrode of complicated shape on the solid electrolyte surface if use the method for above-mentioned spraying noble metal nuclear.
Japan (uncensored) patent disclosure NO4-95766 first discloses following manufacture method: in order to form outer plated film, the electrode that a kind of solution that contains precious metal chemical complex is coated to solid electrolyte forms on the part, heating at high temperature then, other components in this coated solution except noble metal, for example, bonding agent all volatilizees or has decomposed, so have only noble metal nuclear to deposit the part that forms nuclear.
According to up-to-date manufacture method, be with stencil printing, stamped method, dip-dye printing, roll stamped method, dip coating, spraying process, dispenser method, can form the part that forms nuclear in the district at electrode easily with desired shape.
Yet there is following point in this method:
Particularly because the heating plated film carries out under high temperature (for example 700 ℃ or higher), noble metal flocculation deposition causes the average particle size particle size of noble metal nuclear in advance between 0.1 μ～0.8m.Therefore shown in Figure 24 A, noble metal nuclear 92 can not enter and be formed on solid electrolyte 2 lip-deep micropore small ruts 21, and just rests on the porch of micropore small rut 21.
In this case, plated film 119 can not enter micropore small rut 21 shown in Figure 24 B, so can not obtain the adhesion based on the grappling effect between plated film 119 and solid electrolyte 2.
Furthermore, shown in Figure 24 A, noble metal nuclear 92 drops on the surface of solid electrolyte 2 in a kind of manufacture method in back, this means that the distance of 92 of adjacent noble metal nuclears becomes big.Obviously, between the regional plated film 119 of non precious metal nuclear 92 and solid electrolyte 2, do not have adhesion,, on solid electrolyte 2 surfaces, exist tractionless zone in large quantities by a kind of manufacture method in back.
Therefore, in the method for the back oxygen sensing element for example made of a kind of manufacture method, easily generating electrodes is peeled off phenomenon, and the surface resistance between electrode and solid electrolyte 2 interfaces is excessive, to such an extent as to can not export the needed signal of detection oxygen concentration.
An object of the present invention is to provide that a kind of its electrode is difficult for and solid electrolyte is peeled off and electrode and solid electrolyte interface between the little oxygen sensing element of surface resistance.
Another object of the present invention provides a kind of method of making above-mentioned oxygen sensing element.
According to an aspect of the present invention, the oxygen sensing element comprises that there is solid electrolyte and lip-deep electrode that is formed on this solid electrolyte of pit on a kind of surface, and this electrode embeds this pit deeply to guarantee the closely grappling of surface of electrode and solid electrolyte.
Can design this electrode for through being arranged on the plated film that the lip-deep noble metal karyomorphism of solid electrolyte becomes, little being enough to of this noble metal nuclear mean diameter makes it can embed pit dearly.
The mean diameter of above-mentioned this noble metal nuclear is 0.05 μ m or littler.
On above-mentioned each pit more small rut is arranged, electrode can further embed this littler pit.
According to another aspect of the present invention, manufacturing comprises that a kind of its surface has the solid electrolyte of pit and a method that is formed on the oxygen sensing element of the lip-deep electrode of this solid electrolyte to comprise the following steps: the electrode that a kind of solution that contains the precious metal chemical complex that forms nuclear is coated in solid electrolyte is formed on the surface in zone, so that form a coated film, to this coated film heating, noble metal nuclear is separated out, to form the zone of nuclear; The person of connecing is to this regional plated film that forms nuclear, and this coatings embeds pit dearly; This plated film of sintering is to form electrode then, and electrode embeds these pits dearly like this.
Above-mentioned noble metal nuclear has enough little mean diameter, so that its dark embedding in the pit.
The mean diameter of above-mentioned this noble metal nuclear is 0.05 μ m or littler.
Above-mentioned coated film is heat-treated under 200 ℃～600 ℃ temperature.
Above-mentioned precious metal chemical complex is a kind of organic compound of noble metal.
For the degree of irregularity that improves the surface has been done concavo-convex processing on the solid electrolyte surface.
The concentration of precious metal chemical complex is 0.05～0.4% (weight ratio) in the solution.
Noble metal in the above-mentioned precious metal chemical complex has a kind of Pt of being selected from, Pd, Au and Rh at least.
With reference to accompanying drawing, can more fully understand the present invention in conjunction with following detailed description
In the accompanying drawings:
Figure 1A is the enlarged drawing on the solid electrolyte surface of oxygen sensing element among first embodiment of the present invention;
Figure 1B is formed in the enlarged drawing of the lip-deep plated film of solid electrolyte shown in Figure 1A;
Fig. 1 C is formed in the enlarged drawing of lip-deep micropore of the solid electrolyte shown in Figure 1B or pit;
Fig. 2 A is the front view of the oxygen sensing element of first embodiment of the present invention;
Fig. 2 B is the longitudinal sectional drawing of the oxygen sensing element shown in Fig. 2 A;
Fig. 3 is the end cross sectional view of the oxygen sensing element shown in Fig. 2 A and the 2B;
Fig. 4 A is the front view of nozzle that is used for forming electrode thereon of first embodiment of the invention;
Fig. 4 B is the side diagrammatic sketch of the nozzle shown in Fig. 4 A;
Fig. 5 A is follow-on front view of nozzle shown in Fig. 4 A and the 4B;
Fig. 5 B is the side view of the nozzle shown in Fig. 5 A;
Fig. 6 is the longitudinal sectional drawing of the oxygen sensing element of first embodiment of the invention;
Fig. 7 A is follow-on front view of the oxygen sensing element of first embodiment of the invention;
Fig. 7 B is the longitudinal sectional drawing of the oxygen sensing element shown in Fig. 7 A;
Fig. 8 is the transverse cross-sectional view of the end face of the oxygen sensing element shown in Fig. 7 A and the 7B;
Fig. 9 is the follow-on front view of oxygen sensing element of first embodiment of the present invention;
Figure 10 A is the follow-on front view of oxygen sensing element of first embodiment of the present invention;
Figure 10 B is the longitudinal sectional drawing of the oxygen sensing element shown in Figure 10 A;
Figure 11 A is the follow-on front view of oxygen sensing element of first embodiment of the present invention;
Figure 11 B is the longitudinal sectional drawing of oxygen sensing element shown in Figure 11 A;
Figure 12 A is the follow-on front view of oxygen sensing element of first embodiment of the present invention;
Figure 12 B is the longitudinal sectional drawing of oxygen sensing element shown in Figure 12 A;
Figure 13 is the horizontal enlarged drawing of the external electrode of the oxygen sensing element shown in Figure 12 A and the 12B;
Figure 14 A is the follow-on front view of oxygen sensing element of first embodiment of the present invention;
Figure 14 B is the longitudinal sectional drawing of the oxygen sensing element shown in Figure 14 A;
Figure 15 A is the follow-on front view of oxygen sensing element of first embodiment of the present invention;
Figure 15 B is the longitudinal sectional drawing of the oxygen sensing element shown in Figure 15 A;
Figure 16 is the transverse cross-sectional view of the end of the oxygen sensing element shown in Figure 15 A and Figure 15 B;
Figure 17 is the longitudinal sectional drawing of end of the oxygen sensing element of aforementioned second embodiment;
Figure 18 is follow-on longitudinal sectional drawing of the oxygen sensing element of aforementioned second embodiment;
Figure 19 is that the modified of oxygen sensing element of aforementioned second embodiment is at the sectional drawing of solid electrolyte and electrode and electrode and protective seam interface;
Figure 20 is the front view of the oxygen sensing element of aforementioned the 3rd embodiment;
Figure 21 is the longitudinal sectional drawing of the end of oxygen sensing element shown in Figure 20;
Figure 22 is the front view of the lamination oxygen sensing element of aforementioned the 4th embodiment;
Figure 23 is the transverse cross-sectional view of oxygen sensing element shown in Figure 22;
Figure 24 A is the enlarged drawing on surface of the solid electrolyte of conventional oxygen sensing element;
Figure 24 B is formed in the enlarged drawing of the lip-deep plated film of the solid electrolyte shown in Figure 24 A;
Below in conjunction with description of drawings the preferred embodiments of the present invention, same in the present invention same thing of symbology or correlative.
First embodiment:
Below with reference to Figure 1A to Fig. 6 aforementioned first embodiment is described.
Be to make oxygen sensing element 1, will contain the formation electrode that the noble metal compound solution that forms nuclear is coated in solid electrolyte 2 and form on the zone, form coated film.
Then, the coated film heating is examined the part that is formed with nuclear 20 of 22 depositions to be formed with noble metal, as Figure 1A (synoptic diagram that is formed with the part 20 of nuclear).For ease of deposition on solid electrolyte 2, noble metal nuclear 22 is noble metal structures of ball-type or dome-type, this structure is through the heat treated to coated film, the precious metal chemical complex that is included in the solution is decomposed on the surface that is deposited on solid electrolyte 2 obtain.
Then, metal coating being added on the part 20 that is formed with nuclear, is in order to form plated film 119 thereon.After this plated film 119 is sintered and just obtains above-mentioned electrode 11 and 12.
The mean diameter of the noble metal nuclear 22 on the part 20 that is formed with nuclear is 0.05 μ m or littler.
Be the detailed description of oxygen sensing element 1 below:
To shown in Figure 3, be closed formation reference air chamber 13 as Fig. 2 A in solid electrolyte 2 its ends.Solid electrolyte 2 is made by zirconia.As mentioned above, external electrode 11 is attached to the cylindrical outer surface of solid electrolyte 2, and interior electrode 12 is attached to the cylindrical form interior surface of solid electrolyte 2.Cylindrical form interior surface surrounds reference air chamber 13.
One annular element 29 that radially outwards protrudes is arranged on the cylindrical outer surface of solid electrolyte 2, form the secondary ladder on the top of annular element 29 and make annular element 29 become parts with three kinds of different-diameters.
Shown in Fig. 2 A, external electrode 11 is produced on 201 places, end of solid electrolyte 2, is bar shaped.Shown in Fig. 2 B, interior electrode 12 is produced on the cylindrical form interior surface that surrounds on reference air chamber 13 and that part corresponding with external electrode 11.External electrode 11 is connected with electrode terminal 111 usefulness leads via the upwardly extending contact conductor 110 of external electrode.Equally, interior electrode 12 is connected with electrode terminal 121 usefulness leads through contact conductor 120, from the upwards expansion of interior electrode 12. Electrode terminal 111 and 121 is in the cast parts 202 of the outside surface of solid electrolyte 2.
Shown in Fig. 7 B, electrode terminal 121 also can be formed on the internal layer surface of solid electrolyte 2.
As shown in Figure 3, contact conductor 110 is paired, and contact conductor 120 also is paired, and contact conductor 110 is upwards placed in pairs in the same footpath of solid electrolyte 2 with 120 and become 180 ° of angles.
On the other hand, as shown in Figure 8, contact conductor 110 and 120 also can be arranged on four Different Diameter upwards, and the angle between per two lead-in wires is 90 ° of placements.As long as can draw signal of sensor, contact conductor 110 or 120 number also can not be 2.
Set the length L 1 of external electrode 11 and the length L 2 of interior electrode 12 and equate that be 10mm, the thickness of setting electrode 11 and 12 is 1 μ m, the width W 1 and the W2 that set contact conductor 110 and 120 are 1.5mm.The length R1 that sets contact conductor 110 is 23mm, and the length R2 of contact conductor 120 is 34mm, and each electrode terminal 111 and 121 is the rectangle of 5mm * 4mm.In addition, as long as can draw signal of sensor, electrode terminal 111 and 121 also can be other arbitrary shape.
The length of L1, L2 preferably is set at 2～20mm.If less than 2mm, then can not obtain required sensor output signal, if greater than 20mm, the output of sensor may comprise the output from (low temperature parts) parts, and the response characteristic of these parts is bad, and this can make the response characteristic of whole sensor become bad.Make to be worth and reduce.
Be explanation below to the lambda sensor 3 that above-mentioned oxygen sensing element 1 is housed
As shown in Figure 6; lambda sensor 3 comprises a shell 30 and the oxygen sensing element 1 in shell 30; one gas compartment to be measured 33 that is surrounded by gas side cover 330 to be measured is arranged at the bottom of shell 30; cover 330 is double-deck; can protect the end 201 of oxygen sensing element 1, tertiary circulation border side cover 31,32,33 is arranged at the top of shell 30.
Rod well heater 34 is installed in the reference air chamber 13 of oxygen sensing element 1, and oxygen sensing element 1 has a clear space that adapts with the inside surface of solid electrolyte 2, and this solid electrolyte 2 has determined the position of reference air chamber 13.
Joint Terminal 383,384 is arranged at the bottom of contact conductor 391～392, and terminal 383,384 is connected with terminal 381,382 usefulness leads on being installed in oxygen sensing element 1, and the electrode terminal 111,121 of terminal 381,382 and aforesaid oxygen sensing element 1 links.
Describe the manufacture method of above-mentioned oxygen sensing element 1 below in detail.
At first zirconia is made the shape shown in Fig. 2 A, 2B, and sintering obtains (ZrO fast
2-Y
2O
3) solid electrolyte 2 of type.As long as can reach certain ionic conductance, solid electrolyte 2 also can be made by other materials.Then, the electrode that the solution that contains precious metal chemical complex is coated to solid electrolyte 2 forms on the inside and outside surface in zone, to form coated film.Shown in Fig. 2 A, 2B.
Precious metal chemical complex can use organic compound such as the dibenzylidene platinum (C of Pt
16H
16Pt).In aforesaid solution, wherein the content of the organic compound of Pt is 0.4% (weight ratio).The organic compound beyond the region of objective existence of removing platinum in solution also contains acroleic acid binding agent and terpilenol.
The dispenser method is used for this solution is coated in the electrode formation part of cylindrical form interior surface, on the other hand, for aforementioned solution is coated on the cylindrical outer surface, repeatedly contaminate printing.
Used the nozzle 4 (shown in Fig. 4 A, 4B) with internal channel in above-mentioned dispenser method, bend at an angle of 90 the end 41 of nozzle 4, and the heart is processed with the filling orifice 410 that an injection solution is used therein.
At first, nozzle 4 is inserted in the solid electrolytes 2, and near the bottom of reference air chamber 13.In the process of inserting nozzle 4, the electrode that solution is applied to one of contact conductor 120 forms on the part.Then, further this solution of coating on this position, simultaneously, vertically also the edge applies so that finish the solution of interior electrode 12 with respect to the end 41 of the annular movement nozzle 4 of the cylindrical inside circumference of solid electrolyte.
Then, in end 41 sprayed solution, to the top of reference air chamber 13 moving nozzle 4 by nozzle 4.At this moment, not around the end 41 of the cylindrical form interior surface moving nozzle 4 of solid electrolyte 2.
By above operation, finished electrode 12 and contact conductor in this solution is coated to the electrode of 120 (see figure 3)s has been formed task on the part.
After this, the electrode that solution is coated to lead portion 129 forms district's (seeing Fig. 2 A), corresponding electrode lead-in wire 120 is drawn out to the cylindrical outer surface of solid electrolyte 2, and at the cylindrical outer surface formation electrode terminal 121 of solid electrolyte 2 near the upper part, then, finish the coating of this solution.
The nozzle 4 that can use the nozzle 4 shown in Fig. 5 A and 5B to replace shown in Fig. 4 A, 4B.Nozzle 4 ends shown in Fig. 5 A, the 5B comprise a porous member 42, pass the hole of porous member 42, and solution is injected and will be coated to electrode and form on the part.
Then the coated film that electrode is formed on the part is done dried.
Then, under 400 ℃ temperature, coated film is heat-treated, the organo-platinic compounds that is included in the coated film is decomposed, form the zone so that make noble metal nuclear (for example platinum nuclear) be deposited on aforesaid electrode, simultaneously, remove other composition by volatilization and decomposition, as bonding agent.
By aforesaid operations, shown in Figure 1A to 1C, like that, formed the part 20 that is formed with nuclear, in these parts, noble metal nuclear 22 is scatter equably and is embedded dearly in a large amount of lip-deep micropore or pit 21 that are formed on solid electrolyte 2.
Then, shown in Figure 1B, the part 20 that is formed with nuclear is carried out chemically plating platinum, form plated film 119.Plated film 119 can be by the noble metal beyond the platinum, and for example palladium (Pd), gold (Au) and rhodium (Rh) constitute.The material that constitutes plated film needn't be same with the noble metal nuclear phase.When plated film, noble metal nuclear 22 and the noble metal reaction that is contained in the plated film soup are so that help forming plated film 119.Because noble metal nuclear 22 dark embeddings in the small ruts 21, and then coating liquid and plated film 119 also go deep into small rut 21.After this, plated film 119 and solid electrolyte 2 1000 ℃ of following heat-agglomeratings obtaining external electrode 11, interior electrode 12, contact conductor 110,120 and electrode terminal 111,121, they all embed in the small rut 21 deeply.
Can obtain the described oxygen sensing element 1 of first embodiment of the present invention through aforesaid operations.
As mentioned above, on the surface of solid electrolyte 2 just like a large amount of small rut 21 shown in Figure 1A, on the other hand, as mentioned above, the mean diameter of the noble metal nuclear 22 that forms under aforementioned operation is not more than 0.05 μ m, it is also more much smaller than small rut 21, so noble metal nuclear 22 can embed in the small rut 21 deeply.In addition, as Fig. 1 best image that C does, noble metal nuclear 22 even can embed in the micropore 210 in the small rut 21.
Furthermore, 22 of adjacent noble metal nuclears very little apart from d this means to form the part 20 that is formed with nuclear, can not make noble metal nuclear 22 concentrate on a certain zone, forms on the part and will make it be evenly dispersed in entire electrode.
Because this reason because the strong adhesive force that on the interface between plated film 119 and the solid electrolyte 2, is obtained, be formed on that each plated film 119 on the zone 20 that is formed with nuclear can be firm attached on the solid electrolyte 2.Therefore, between solid electrolyte 2 and each external electrode 11 that is obtained by sintering plated film 119 and interior electrode 12, can obtain very strong bounding force.Therefore, external electrode 11 and interior electrode 12 can peel off hardly from the surface of solid electrolyte 2.
Furthermore, because noble metal nuclear 22 distributes on the part 20 that is formed with nuclear equably, above-mentioned powerful adhesion is in whole solid electrolyte 2 and external electrode 11 and 12 existence of interior electrode.The surface resistance of its interface is very little like this, contact conductor 110 and 120, and electrode terminal 111 also is identical with 121 situation.
In aforementioned first embodiment, be with dispenser method and dip-dye print process solution to be coated to electrode to form on the part.At stencil printing, stamped method, roll and have at least a kind of method also to can be used to electrode is formed the part coating in stamped method, dip coating and the spraying process.
Recommend to use the dip-dye print process, roll stamped method.Because it at a curved surface cylindrical surfaces externally and internally of cylindric solid electrolyte for example, form the coated film of required form easily, and this coated film can reach higher precision.
In aforesaid first embodiment, the thermal treatment of coating film is carried out under 400 ℃, be preferably under 200～600 ℃ and carry out.
When this temperature is higher than 600 ℃, the flocculation of noble metal can take place, thereby cause noble metal to form the mean diameter＞0.05 μ m in the zone of nuclear.Follow the flocculation of noble metal, noble metal is endorsed and can be focused on a certain zone, thereby causes electrode and solid electrolyte to be peeled off.
When this temperature was lower than 200 ℃, in fact precious metal chemical complex did not decompose.The deposition of noble metal nuclear does not take place, and just can not be formed with the part of nuclear yet.In fact, plated film just can not cause the part of solid electrolyte to be exposed to the outside attached on the solid electrolyte yet.And then be that the carbon that the component of other except that precious metal chemical complex or these components produce in the solution remains on the solid electrolyte surface.Just do not had very strong adhesion between noble metal nuclear and the solid electrolyte so yet.
In aforementioned first embodiment, the noble metal that forms nuclear in precious metal chemical complex is platinum (Pt).It is at least a that the noble metal that forms nuclear in precious metal chemical complex is preferably selected among Pt, Pd, Au and the Rh.These metal pair plated films play catalytic action, can make and form extraordinary plated film on the solid electrolyte.As aforementioned first embodiment, preferably using organic precious metal chemical complex.The viscosity of the conveniently adjusted solution of this organic precious metal chemical complex is so the easier electrode that makes solution be coated in solid electrolyte forms on the part.
In aforementioned first embodiment, the content of organic Pt compound is 0.4% (weight ratio) in the solution.The content of precious metal chemical complex is preferably between 0.05～0.4% (weight ratio).
When the amount of this concentration precious metal chemical complex during less than 0.05% (weight ratio) very little, so be difficult for being formed with the part that is formed with nuclear of equally distributed noble metal nuclear.Plated film and solid electrolyte just do not have very strong adhesion yet like this, electrode easily and solid electrolyte peel off.
On the other hand, when this concentration during greater than 0.4% (weight ratio), the flocculation of noble metal can take place, make the mean diameter＞0.05 μ m of noble metal nuclear.Follow the flocculation of noble metal, noble metal is endorsed and can be focused on a certain zone, thereby causes electrode and solid electrolyte to be peeled off.
Below to estimating, and comparative sample (oxygen sensing element) is made an explanation by manufactured samples of the present invention (oxygen sensing element) (hereinafter referred to as " invention sample ").
Table one relates to invention sample 1～19, and table two relates to comparative sample 20～28.In sample 1～28, use organic precious metal compounds as precious metal chemical complex.When noble metal is Pt, use dibenzylidene platinum (C
16H
16Pt), and when noble metal is Pd, use face cream palladium (C as organo-platinic compounds
10H
18SPdClx is x=1～3 wherein) as organic precious metal compounds.
According to resistance value test and degree of peeling off test evaluation sample 1～28.
Direct current resistance when each sample resistance value is 400 ℃ between internal and external electrode.
Peeling off test is to adhere to an adhesive tape on external electrode, peels off this adhesive tape then, peel off this adhesive tape after, external electrode is carried out both macro and micro observes, peel off if under both macro and micro is observed, there is no external electrode, in table 1 and table 2, fill out 0.
What macroscopic observation was used is magnifier, and what microscopic observation was used is scanning electron microscope.
Provided the evaluation result of sample 1～28 below.
On the other hand, comparative sample 20～28 all presents high value, and the result of disbonded test is also bad.
Can reach a conclusion thus: each oxygen sensing element of sample of the present invention, its electrode are difficult for peeling off with solid electrolyte, and the surface resistance of its electrode and solid electrolyte intersection is very little, can guarantee to be used for oxygen concentration and detect necessary output signal.
As shown in table 3, precious metal chemical complex also can adopt inorganic precious metal chemical complex, and the concentration of noble metal is 0.4% (weight ratio) in the solution of each invention sample 29～30, and heat treated temperature is 400 ℃.The characteristics identical with invention sample 1～19 in the table 1, that the invention sample 29 and 30 in the table 3 also presents low resistance and is difficult for peeling off.Table 1
Table 2
*1。Because residual bonding agent is energy measurement * 2 not.Because too much stripping electrode resistance value is ∞
| Sample number | Noble metal | The mean diameter (μ m) of noble metal nuclear | Precious metal concentration (%wt) | Heat treatment temperature (℃) | Resistance value (K Ω) | Disbonded test |
| 1 | Pt | 0.01 | 0.4 | 400 | 9 | O |
| 2 | Pt | 0.007 | 0.1 | 200 | 10 | O |
| 3 | Pt | 0.01 | 0.05 | 600 | 9 | O |
| 4 | Pt | 0.005 | 0.05 | 200 | 10 | O |
| 5 | Pt | 0.04 | 0.4 | 400 | 11 | O |
| 6 | Pt | 0.03 | 0.1 | 600 | 9 | O |
| 7 | Pt | 0.006 | 0.1 | 200 | 11 | O |
| 8 | Pt | 0.008 | 0.05 | 400 | 10 | O |
| 9 | Pt | 0.08 | 0.4 | 600 | 11 | O |
| 10 | Pd | 0.008 | 0.4 | 200 | 11 | O |
| 11 | Pd | 0.01 | 0.1 | 400 | 10 | O |
| 12 | Pd | 0.01 | 0.05 | 600 | 10 | 0 |
| 13 | Pd | 0.005 | 0.05 | 200 | 9 | O |
| 14 | Pd | 0.03 | 0.4 | 400 | 10 | O |
| 15 | pd | 0.05 | 0.1 | 600 | 9 | 0 |
| 16 | Pd | 0.007 | 0.1 | 200 | 10 | O |
| 17 | Pd | 0.01 | 0.06 | 400 | 10 | O |
| 18 | Pd | 0.09 | 0.4 | 600 | 12 | O |
| 19 | Rh | 0.01 | 0.4 | 400 | 10 | O |
| Sample number | Noble metal | The mean diameter (μ m) of noble metal nuclear | Precious metal concentration (%wt) | Heat treatment temperature (℃) | Resistance value (K Ω) | Disbonded test |
| 20 | Pt | *1 | 0.4 | 100 | *2 | X |
| 21 | Pt | 0.11 | 0.4 | 700 | 32 | X |
| 22 | Pd | 0.15 | 0.4 | 900 | *2 | X |
| 23 | Pd | *1 | 0.4 | 100 | *2 | X |
| 24 | Pd | 0.12 | 0.4 | 700 | 96 | X |
| 25 | Pt | 0.18 | 0.4 | 900 | *2 | X |
| 26 | Pt | 0.001 | 0.01 | 600 | *2 | X |
| 27 | Pt | 0.12 | 0.6 | 600 | 30 | X |
| 28 | Rh | 0.15 | 0.4 | 900 | *2 | X |
Table 3
| Sample number | Precious metal chemical complex | The mean diameter (μ m) of noble metal nuclear | Resistance value (K Ω) | Disbonded test |
| 29 | H 2PtCl 6 | 0.005 | 9 | |
| 30 | The Pt particle | 0.05 | 12 | O |
In aforementioned first embodiment, the upside that the solid electrolyte 2 of oxygen sensing element 1 is formed in protruding dish 29 has two-stage ladder such shown in Fig. 2 A and 2B; On the other hand, as shown in Figure 9, solid electrolyte 2 has only the one-level ladder on the top of protruding dish 29; Perhaps solid electrolyte does not have ladder can use yet.
Be a modified of the oxygen sensing element 1 of aforementioned first embodiment shown in Figure 10 A and the 10B, the structure in each electrode formation district on the solid electrolyte 2 all is different from aforementioned first embodiment therein.
Specifically, shown in Figure 10 A, the outside surface that plated film covers solid electrolyte 2 comprises on the scope of top 201 and main body 202, so that form a cup-shaped external electrode 11, cylindrical electrode lead-in wire 110 and cylindrical electrode terminal 111.On the other hand, shown in Figure 10 B, the whole cylindrical form interior surface of solid electrolyte 2 forms one deck plated film, and the result has formed cup-shaped interior electrode 12, cylindrical electrode lead-in wire 120 and cylindrical electrode terminal 121.
Other structure is as described above shown in first embodiment.
Be a modified of the oxygen sensing element 1 of aforementioned first embodiment shown in Figure 11 A and the 11B, the electrode of each solid electrolyte 2 forms partly slightly different with aforementioned first embodiment here.
Specifically, implement to compare with aforementioned first shown in Figure 11 A, external electrode 11 has covered the top 201 of whole solid electrolyte 2 at cylindrical outer surface.Shown in Figure 11 B, interior electrode 12 has covered entire top 201 at its cylindrical form interior surface equally, and has further formed electrode terminal 121 at the cylindrical form interior surface of solid electrolyte 2.
Other is partly identical with aforementioned first enforcement.
Shown in Figure 12 A, the 12B and 13 is the modified of the aforementioned first embodiment oxygen sensing element, and it is slightly different that each electrode on the solid electrolyte 2 forms regional structure and aforementioned first embodiment.
Specifically, shown in Figure 12 A, external electrode 11 is grid-shaped; Shown in Figure 12 B, interior electrode 12 also is a grid-shaped, and electrode terminal 121 is on the cylindrical form interior surface of solid electrolyte 2.
Other structure is identical with aforementioned first embodiment.
Shown in Figure 14 A and the 14B is the modified of the oxygen sensing element of aforementioned first embodiment, and it is slightly different that wherein the electrode on each solid electrolyte 2 forms regional structure and aforementioned first embodiment.
Specifically, shown in Figure 14 A and 14B, the length of external electrode 11 and interior electrode 12 is the length L 1 of former electrodes 11,12, half of L2, and electrode terminal 121 is on the cylindrical form interior surface of solid electrolyte 2.Other structure is identical with aforementioned first embodiment.
Shown in Figure 15 A, the 15B and 16 is the modified of the oxygen sensing element of aforementioned first embodiment, and it is slightly different that wherein each electrode on the solid electrolyte 2 forms regional structure and aforementioned first embodiment.
Specifically, contact conductor group 110 quantity of drawing from external electrode 11 expand to 4, the quantity of drawing equally from the contact conductor group 120 of interior electrode 12 also expands to 4, and electrode terminal 121 is on the cylindrical form interior surface of solid electrolyte 2, and other structure is identical with aforementioned first embodiment.
In the modified shown in Figure 10 A and 10B,,, help producing this oxygen sensing element so can realize forming the zone that is formed with nuclear at an easy rate because electrode forms district's simple shape.
In the modified shown in Figure 11 A, 11B, because electrode forms the zone and cover entire top 201 on cylindrical inside and outside surface, the formation mask operation step of this part that is formed with nuclear because of the formation of the part that is formed with nuclear can part omission, make the production that helps this oxygen sensing element.
In the modified shown in Figure 12 A, 12B and 13, external electrode 11 and interior electrode 12 all are net forms, and oxygen is improved to the diffusion of solid electrolyte 2, and the response characteristic of oxygen sensing element 1 is fine like this.
In the modified shown in Figure 14 A and 14B, can reduce the consumption of noble metal.
In the modified shown in Figure 15 A, 15B and 16, even a pair of breaking down arranged in contact conductor 110 and 120, the output of sensor is still and can obtains needed sensor output signal.
Second embodiment:
With reference to Figure 17 second embodiment of the present invention is described:
As shown in figure 17, oxygen sensing element 1 comprises external electrode 11 similar to the modified shown in Figure 11 A, the 11B and interior electrode 12.On external electrode 11, form first protective seam 191 in addition, so that cover whole external electrode 11.
First protective seam 191 also has a kind of function of diffusion impervious layer.Its thick 100 μ m porosity 20% is by the MgAl that obtains by plasma sputtering
2O
4Spinel is formed.
Another structure is identical with aforementioned first embodiment.
In a second embodiment, because first protective seam 191 is arranged on the surface of external electrode 11, the external electrode 11 of oxygen sensing element 1 has good durability.
Figure 18 illustrates the oxygen sensing element modified of aforementioned second embodiment, also is included in second protective seam 192 that forms above first protective seam 191 at modified oxygen sensing element 1 shown in Figure 180.Second protective seam, 192 thick 120 μ m, porosity 20～50% is by Al
2O
3Form.
Specifically, by with Al
2O
3Become slurry, utilize the dip coating Al that becomes slurry
2O
3Apply the outside surface of first protective seam 191, then it is heat-treated, form second protective seam 192.
Other structures are identical with aforementioned second embodiment.
In the improvement shown in Figure 180, remove outside aforementioned second embodiment, owing to there is second protective seam 192 to obtain the effect of gatherer.Like this, the durability of the outer electrode 11 of oxygen sensing element 1 is better.
As shown in figure 19, for improving the degree of irregularity on solid electrolyte 2 surfaces, preferably concavo-convex processing is done on its surface.By above-mentioned processing, make the degree of irregularity on solid electrolyte 2 surfaces improve, the contact area between solid electrolyte 2 and plated film increases, and more noble metal nuclear contacts with plated film, and, chimeric dearly at the irregular place on the surface of plated film and solid electrolyte 2.Like this, will between solid electrolyte 2 and plated film, produce a kind of very strong bonding force.The situation of electrode also is like this.From Fig. 19, the surface of solid electrolyte 2 irregular not only increases the bonding force of 11 of solid electrolyte 2 and external electrodes, and increases the bonding force between the external electrode 11 and first protective seam 191.Like this, the oxygen sensing element 1 with excellent durability has just manufactured.Above-mentioned concavo-convex processing can be adopted burn into coating powder, heat spray or similar method.
The 3rd embodiment:
Below with reference to Figure 20,21 third embodiment of the present invention is described.
Shown in Figure 20,21, oxygen sensing element 1 comprises a separation layer 17.In order to make oxygen sensing element 1 with separation layer 17, be formed with the part of nuclear at solid electrolyte 2 column type outside surfaces, its scope from the end of end piece 201 to the A part of main element 202.Form plated film being formed with on the part of nuclear then.
Then, as shown in figure 20, form by MgAl in those parts except that being used as the end 201 of outer electrode 11 and on plated film
2O
4Spinel or Al
2O
3The separation layer 17 that is constituted.
Then, on separation layer 17, form contact conductor 110 and electrode terminal 111, so that electrically connect (as shown in figure 21) with the plated film of end piece 201.
Then, obtain oxygen sensing element 1 by this solid electrolyte of sintering.
Other structure is identical with the first above-mentioned embodiment.
In the oxygen sensing element 1 among the 3rd embodiment, because those relatively poor parts of response characteristic are covered by separation layer 17, the sensor output signal that produces from these parts is not included in total sensor output, therefore generally speaking, can obtain fabulous response characteristic.
The 4th embodiment:
Below with reference to Figure 22,23 fourth embodiment of the present invention is described.
Shown in Figure 22,23, the 4th embodiment is relevant with stacked oxygen sensing element 5, and stacked oxygen sensing element 5 comprises a dull and stereotyped solid electrolyte 2 with outer electrode 11 and internal electrode 12.
The method that outer electrode 11 is identical with aforementioned first embodiment with internal electrode 12 usefulness is made.Electrode at dull and stereotyped solid electrolyte 2 forms the part that is formed with nuclear on the part earlier, forms plated film then on the zone of this formation nuclear, last this plated film of sintering.
Form the outside of the solid electrolyte 2 of outer electrode 11 therein, and generate first and second protective seams 191 and 192 according to the order of sequence.
Form the inboard of the solid electrolyte 2 of internal electrode 12 therein, be provided with and comprise having the heater plates 59 that atmosphere is introduced passage and well heater 58.
Other structure is identical with aforesaid first embodiment.
As seen, the present invention also can be applied on the stacked oxygen sensing element 5, and stacked oxygen sensing element 5 in the present embodiment has identical effect with oxygen sensing element among aforementioned first embodiment.The present invention can further be applied on the stacked oxygen sensing element of two chambers (two-cell) type, and some electrodes are corresponding to some solid electrolyte settings in this element.
Though described the present invention in a preferred embodiment, the present invention is not limited to this, can also in following claim, limit, implement in the multiple mode that does not deviate from principle of the present invention.
Claims (6)
1. oxygen sensing element, this element comprises:
One has pit on its surface, and the solid electrolyte of littler pit is arranged in each described pit; With
An electrode that on the surface of this solid electrolyte, forms, described electrode produces by noble metal nuclear with the plated film form, the average particulate diameter of described noble metal nuclear is 0.05 μ m or littler and only form on the surface of this solid electrolyte so that make this noble metal nuclear embed described pit and further in the described littler pit of embedding, causing this electrode to embed this pit and further to embed in the described littler pit, with the bonding force on the surface of guaranteeing this electrode and this solid electrolyte.
2. method of making the oxygen sensing element, this oxygen sensing element comprises: a solid electrolyte and an electrode that forms on the surface of this solid electrolyte.This method comprises the following steps:
The electrode that a kind of solution that contains a kind of organic precious metal compounds of karyomorphism one-tenth is coated to this solid electrolyte forms on the surface of part, to form coated film;
By heating, described coated film is heat-treated, become part so that deposit the karyomorphism of organic precious metal nuclear in the pit that forms and the littler pit that further forms in each described pit on the surface of this solid electrolyte, the average particulate diameter of described organic precious metal nuclear is 0.05 μ m or littler;
Described karyomorphism is become the part plated film, so that form plated film, this plated film embeds described pit and further embeds in the described littler pit;
The described plated film of sintering is to form described electrode, so that make described electrode embed described pit and further the embedding in the described littler pit.
3. method as claimed in claim 2 is characterized in that: described coated film is heat-treated under 200～600 ℃.
4. method as claimed in claim 2 is characterized in that: concavo-convex processing is done on the surface of described solid electrolyte, so that improve this surperficial degree of irregularity.
5. method as claimed in claim 2 is characterized in that: the concentration of precious metal chemical complex is 0.05 weight %～0.4 weight % in the described solution.
6. method as claimed in claim 2 is characterized in that: the noble metal in this precious metal chemical complex has a kind of Pt of being selected from, Pd, Au, Rh at least.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP150255/96 | 1996-05-21 | ||
| JP150255/1996 | 1996-05-21 | ||
| JP15025596A JP3811991B2 (en) | 1996-05-21 | 1996-05-21 | Oxygen sensor element manufacturing method and oxygen sensor element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1174994A CN1174994A (en) | 1998-03-04 |
| CN1122841C true CN1122841C (en) | 2003-10-01 |
Family
ID=15492953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97114948.8A Expired - Fee Related CN1122841C (en) | 1996-05-21 | 1997-05-21 | Oxygen sensor an making method |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US5948225A (en) |
| EP (1) | EP0809101B1 (en) |
| JP (1) | JP3811991B2 (en) |
| KR (1) | KR100230601B1 (en) |
| CN (1) | CN1122841C (en) |
| DE (1) | DE69727420T2 (en) |
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| JP3956435B2 (en) * | 1997-08-07 | 2007-08-08 | 株式会社デンソー | Oxygen sensor element |
| US6315880B1 (en) | 1997-10-16 | 2001-11-13 | Mary R. Reidmeyer | Chemical plating method, electrolytic cell and automotive oxygen sensor using it |
| DE69814318T2 (en) * | 1997-11-20 | 2004-04-08 | Denso Corp., Kariya | Solid electrolyte with inner reference chamber and electrodes on inner and outer surfaces |
| JP3643224B2 (en) * | 1997-11-25 | 2005-04-27 | 日本特殊陶業株式会社 | Sensor element electrode forming method |
| JP3541702B2 (en) * | 1998-01-16 | 2004-07-14 | 株式会社デンソー | Ceramic-metal bonded body and method of manufacturing the same |
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| JP4617599B2 (en) * | 2000-08-07 | 2011-01-26 | 株式会社デンソー | Gas sensor element and manufacturing method thereof |
| JP2003107033A (en) * | 2001-07-27 | 2003-04-09 | Denso Corp | Gas sensor |
| JP4204773B2 (en) * | 2001-09-17 | 2009-01-07 | 株式会社日立製作所 | Air-fuel ratio detection device |
| EP1354637B1 (en) * | 2002-04-17 | 2012-04-25 | Denso Corporation | Active liquid applicator for forming active film |
| CN1279349C (en) * | 2002-11-06 | 2006-10-11 | 日本特殊陶业株式会社 | Gas sensor mfg. method |
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-
1996
- 1996-05-21 JP JP15025596A patent/JP3811991B2/en not_active Expired - Fee Related
-
1997
- 1997-05-20 KR KR1019970019573A patent/KR100230601B1/en not_active IP Right Cessation
- 1997-05-21 CN CN97114948.8A patent/CN1122841C/en not_active Expired - Fee Related
- 1997-05-21 US US08/861,226 patent/US5948225A/en not_active Expired - Lifetime
- 1997-05-21 DE DE69727420T patent/DE69727420T2/en not_active Expired - Lifetime
- 1997-05-21 EP EP97108239A patent/EP0809101B1/en not_active Expired - Lifetime
-
1999
- 1999-07-26 US US09/360,147 patent/US6254926B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09304334A (en) | 1997-11-28 |
| EP0809101A2 (en) | 1997-11-26 |
| EP0809101A3 (en) | 1999-11-10 |
| KR100230601B1 (en) | 1999-12-01 |
| EP0809101B1 (en) | 2004-02-04 |
| US5948225A (en) | 1999-09-07 |
| US6254926B1 (en) | 2001-07-03 |
| JP3811991B2 (en) | 2006-08-23 |
| DE69727420T2 (en) | 2004-12-16 |
| CN1174994A (en) | 1998-03-04 |
| DE69727420D1 (en) | 2004-03-11 |
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